Preparation of allyl alcohol and its homologues



allyl alcohol and its homologues. is heated under a reflux condenser, while being of this method, however, is subject to the usual Example 2 disadvantages of processes carried out under 2500. of Osts solution (containing0.l5 g. of pressure. copper) and 50g. of methallyl chloride are added It has now been found that practically comto a solution of 115 g. of potassium carbonate in plete saponification can be obtained without the 500 f water and the mixture heated under a use Of pressure high t mp tur s y yreflux condenser, while being stirred, to 120-130 me out t e sapcnificcticn with alkaline media in c. for two hours. On distillation 1.5 g. of lowt e p se e of metals which form c p boiling material and 37 g. of methallyl alcohol pounds or in the presence of these complex com-- a btained, corresponding to 93% of the pounds themselves. These materials catalyze the theory ith t, th addition of o ts solution sapo fi o reaction and apparently Prevent a yield of only 36% was obtained. Furthermore, the development of disturbing side reactions. if potassium hydroxide re used in place of y 0f t usual alkaline media y be Used; potassium carbonate, 9. yield of only 29% of the in alkaline media are preferred. The process is Patented July 8, 1943 PREPARATION or ALLYL ALCOHOL AND rrs HOMOLOGUES Franz Kiihler, Darmstadt, Germany, assignor to & Haas Company, Philadelphia, Pa.

No Drawing. Application January 12. 1940, Serial No. 313,559. In Germany December 30, 1938 4 Claims. (Cl. 2606 40) y This invention relates to the preparation of carbonate in 500 g. of water. The entire mixture It is known that allyl alcohol and its homostirred, to 80-85 C. On distilling this mixture logues can be made by saponification of allyl 1.5 g. of low-boiling material is obtained and 34 chloride and its homologues by means of alka- 5 g. of allyl alcohol corresponding to 90% of the line saponifying agents. If, however, such a. theory. saponificationis carried out in the usual manner, If potassium hydroxide is used in place of the yields obtained vary from about 30 to about potassium carbonate, somewhat lower yields. 60% of the theory depending upon the choice of (about 80%) are obtained, whereas without the the alkaline medium such as caustic alkalies or 10 addition of the copper powder yields of 33 and. alkali carbonates, if desired with a small addi- 46% respectively are obtained It is to be noted tion of bicarbonate. In view of these poor yields that in the absence of copper powder the yields it has already been suggested that the process obtained with pota hydroxide are greater might be improved by working at high temperathan those with potassium carbonate. tures under pressure. The technical application lli' the preferred compounds, however, are alkaline th r was obtained. By using 3.5 g. of pulverreacting salts, particularly the alkali carbonates. 30 ized electrolytic c pperjn place of 051-33 solution The metals which form complexes and which a yield of 96% was t are operable in the present invention are, for f For the f ll wing experiments a crude t-3 example, cobalt, Zinc, and copper, copper being allyl chloride was used which is obtained by- Particularly suitable- The metals must e used the chlorination of technical isobutylene. It

in finely divided form and during the course of contained 57 f pure methallyl chloride t the reaction go into solution, at least in part, remainder being high bonmg chlorides in the form of complex compounds. The same effect is also obtained in the absence of metals Example 3 if the corresponding complex compounds are em- Ployed. Complex compounds which are soluble 40 10 of me filmgs activated wlth copper fate and 50 g. of crude methallyl chloride were addedto a solution of 100 g. of crystallized sodium carbonate in 500 g. of water and the entire mixture stirred and heated two and one-half (methallyl alcohol) which may be used as aplashours under a reflux condenser at 1204300 C.

helm for acroleln resins or for the preparation on distillation there was obtained 4 g. of

olmethacrolein.

- boiling materials and 20 g. of methallyl alcohol Tne invention may be illustrated by the fol co espond g to of the theorylowing examples but it is not limited to the exact particularly suitable for allyl alcohols substituted in the 2 position, suchas Z-methyl allyl alcohol materials, times, temperatures, etc. indicated as Example 4 it may otherwise be practiced within the scope of the appended claims. 3.5 g. of pulverized electrolytic copper and g. of crude methallyl chloride were added to 9. Example 1 solution of 115 g. of potassium carbonate and 500 3.5 g. of copper powder and 50 g. of allyl chlog. of water and the mixture stirred one hour ride are added to a solution of 117 g. of potassium under a reflux condenser at 120 C. On distillation 22.5 gl'oi methallyl alcohol was obtained corresponding to 100% of the theory.

I claim:

1. The process of preparing allyl alcohol and its homologues from the corresponding chlorides which comprises saponifying said chlorides with an alkaline saponifying agent selected from the group consisting o1 alkali metal hydroxides and carbonates while in the presence of a complex compound formed from a metal from the group consisting of zinc, cobalt, and copper and said alkaline saponii'ying agent.

2. The process of preparing allyl alcoholand its homologues from the corresponding chlorides which comprises saponiiying said chlorides with an alkaline saponifying agent selected from the group consisting of alkali metal hydroxides and carbonates while in the presence of a finely difrom vided metal from the group consisting of zinc, cobalt, and copper, which metal forms in situ a I complex compound.

3. The process of preparing allyl alcohol from allyl chloride which comprises saponiiying allyl chloride with an alkaline saponiiying agent selected from the group consisting of alkali metal hydroxides and carbonates in the presence of finely divided copper which forms in situ a complex copper compound.

4. .The process of preparing methallyl alcohol methallyl chloride which comprises saponitying methallyl chloride with an alkaline saponitying agent selected from the group consisting of alkali metal hydroxides and carbonates in the presence of finely divided copper which forms in situ a complex copper compound.

FRANZ KOHLER. 

